• Macromolecular Research
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• 제13권4호
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• pp.314-320
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• 2005

Crosslinked poly(vinyl alcohol) (PVA) membranes were prepared at various crosslinking temperatures using poly(acrylic acid-co-maleic acid) (PAM) containing different PAM contents. The thermal properties of these PVA/PAM membranes prepared at various reaction temperatures were characterized using differential scanning calorimetry (DSC). The proton conductivity and methanol permeability of PVA/PAM membranes were then investigated as PAM content was varied from 3 to 13 wt%. It was found that the proton and methanol transport were dependent on PAM content in their function both as crosslinking agent and as donor of hydrophilic -COOH groups. Both these properties decreased monotonously with increasing PAM concentration. The proton conductivities of these PVA/PAM membranes were in the range from $10^{-3}\;to\;10^{-2}S/cm$ and the methanol permeabilities from $10^{-7}\;to\;10^{-6}cm^{2}/sec$. In addition, the effect of operating temperature up to $80^{\circ}C$ on ion conductivity was examined for three selected membranes: 7, 9 and 11 wt% PAM membranes. Ion conductivity increased with increasing operating temperature and showed and S/cm at $80^{\circ}C$, respectively. The effects of crosslinking and ionomer group concentration were also examined in terms of water content, ion exchange capacity (IEC), and fixed ion concentration. In addition, the number of water molecules per ionomer site was calculated using both water contents and IEC values. With overall consideration for all the properties measured in this study, $7{\sim}9\;wt%$ PAM membrane prepared at $140^{\circ}C$ exhibited the best performance. These characteristics of PVA/PAM membranes are desirable in applications related to the direct methanol fuel cell (DMFC).

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.282-285
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• 2009

This study presents preparation and characterization of composite membranes based on ionic liquids. The ionic liquids act as water in sulfonated membranes. On the behalf of ionic conduction through ionic liquid inside the membranes, non-aqueous membranes showed Arrenhius dependence on temperature with no external humidification. It was implied that hopping mechanism of proton was dominant in the ionic liquid based membranes. In addition, small angle X-ray (SAXS) studies provided the information on morphology of ionic clusters formed by the interaction between sulfonic acid groups of the polymers and ionic liquids. The SAXS spectra showed matrix peaks, ionomer peaks and Prodo's law for Nafion based composite membranes and only matrix peaks for hydrocarbon based ones. However, ionic conductivity and atomic force microscopy (AFM) images showed the clear formation of ionic clusters of the hydrocarbon based composite membranes. It implies for ionic liquid based high temperature membranes that it is important to use sulfonated polymers as solid matrix of ionic liquid which can form clear ionic clusters in SAXS spectra.

• 멤브레인
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• 제7권2호
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• pp.49-56
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• 1997

In order to understand the formation of polymeric membranes or microcellular foams, phase separation phenomena in polymer solutions should be understood. The present review examines the progress made in the understanding of these phenomena, with emphasis on selected polymer-solvent systems. In the case of polymer-solvent systems, coarsening is of particular importance as it may come to dominate or overshadow spinodal decomposition effects within the first minute or few minutes of phase separation. In this article, some of the most important theoretical models of late stage of phase separation are reviewed, and recent experimental studies on coarsening in polymer-solvent systems are studied.

• Macromolecular Research
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• 제11권3호
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• pp.163-171
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• 2003

For the pervaporation of water-ethanol mixtures, new composite membranes having poly(acrylic acid)-poly (butyl methacrylate-co-methyl methacrylate) interpenetrati ng polymer network [PAA-P(BMA-co-MMA) IPN] skin layer supported on porous and crosslinked poly(BMA-co-MMA) were prepared. The morphology of the sub-layer of the composite membrane prepared in the presence of 60 wt% solvent showed cellular structure, on the other hand that of sublayer prepared in the presence of 70 wt% solvent presented very porous interconnected pore structure with macrovoids. Permeation rates of the composite membranes were largely influenced by the morphology of the sublayer. Separation factors increased with the increase of the degree of crosslinking of the PAA network. It was found that permeation rates could be increased by introducing anionic charges on carboxyl groups of the PAA. The permeation rate changes of the PAA-P(BMA-co-MMA) IPN composite membranes according to the feed compositions showed quite similar pattern with the swelling behavior in water-ethanol mixtures.

• Korean Membrane Journal
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• 제6권1호
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• pp.55-60
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• 2004

In recent years, an increasing interest in membrane technology has been observed in chemical and environmental industry. Membrane technology has advantages of low cost, energy saving and environmental clean technology comparing to conventional separation processes. Pervaporation is one of new advanced membrane technology applied for separation of azeotropic mixtures, aqueous organic mixtures, organic solvent and petrochemical mixtures. Sodium alginate composite membranes were prepared for the enhancement of long-term stability of pervaporation performance of water-ethanol mixture using pervaporation. Sodium alginate membranes were crosslinked with CaCl$_2$ and coated with polyelectrolyte chitosan to protect washing out of calcium ions from the polymer. The surface structures of PAN and hydrolysed PAN membrane were confirmed by ATR Fourier transform infrared (FT-IR). A field emission scanning electron microscopy (FE-SEM; Jeol 6340F) operated at 15 kV. Concentration profiles for Ca in the membrane surface and membrane cross-section were taken by an energy dispersive X-ray (EDX) analyser (Jeol) attached to the field emission scanning electron microscopy (Jeol 6340F). Pervaporation experiments were done with several operation run times to investigate long-term stability of the membranes.

• Korean Membrane Journal
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• 제10권1호
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• pp.20-25
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• 2008

Proton conducting composite membranes were prepared by solution blending of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(sulfopropyl methacrylate) (P(VDF-CTFE)-g-PSPMA) graft copolymer and heteropolyacid (HPA). The P(VDF-CTFE)-g-PSPMA graft copolymer was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of P(VDF-CTFE). FT-IR spectroscopy revealed that HPA nanoparticles were incorporated into the graft copolymer via hydrogen bonding interactions. The water uptake of membranes continuously decreased with increasing HP A concentration up to 45wt%, after which it slightly increased. It is presumably due to the decrease in number of water absorption sites due to hydrogen bonding interaction between the HP A particles and the polymer matrix. The proton conductivity of membranes increased with increasing HPA concentration up to 45wt%, resulting from both the intrinsic conductivity of HP A particles and the enhanced acidity of the sulfonic acid of the graft copolymer.

• 전기화학회지
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• 제19권2호
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• pp.45-49
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• 2016

양이온 교환막 연료전지 운전 중에 발생하는 하이드록시 라디칼에 의한 전해질 막의 산화분해를 효과적으로 방지하기 위해 유기물 라디칼냐��쳐를 도입하였다. 술폰화 폴리아릴렌에테르술폰 고분자를 이용하여 폴리페놀 화합물의 일종인 루틴을 도입하여 복합막을 제조하였고, 제조된 고분자 전해질 복합막은 함수율 및 이온전도도의 측정을 통하여 루틴이 전해질 막의 물리화학적 성질에 미치는 영향에 대해서 조사하였다. 실제 연료전지 운전과 유사한 조건을 구현할 수 있는 과산화수소 폭로 가속화 평가장치를 이용하여 전해질 복합막의 산화안정성을 평가하였다. 루틴을 함유한 고분자 전해질 복합막은 이온전도도가 유지되면서 산화안정성이 향상된 결과를 보여주었다.

• 한국수소및신에너지학회논문집
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• 제27권6호
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• pp.660-669
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• 2016

A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• 한국분말야금학회:학술대회논문집
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• 한국분말야금학회 2006년도 Extended Abstracts of 2006 POWDER METALLURGY World Congress Part 1
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• pp.487-488
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• 2006

Novel bisphenol-based wholly aromatic poly(ether sulfone-ketone) copolymer containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of 4,4-difluorobenzophenone, 2,2'-disodiumsulfonyl-4,4'-fluorophenylsulfone (40mole% of bisphenol A) and bisphenol A. Polymerization proceeded quantitatively to high molecular weight in N-methyl-2-pyrrolidinone at $180^{\circ}C$. Organic-inorganic composite membranes were obtained by mixing organic polymers with hydrophilic $SiO_2$ (ca. 20nm) obtained by sol-gel process. The polymer and a series of composite membranes were studied by FT-IR, $^1HNMR$, differential scanning calorimetry (DSC) and thermal stability. The proton conductivity as a function of temperature decreased as $SiO_2$ content increased, but methanol permeability decreased. The nano composite membranes were found to posse all requisite properties; Ion exchange capacity (1.2meq./g), glass transition temperatures $(164-183\;^{\circ}C)$, and low affinity towards methanol $(4.63-1.08{\times}10^{-7}\;cm^2/S)$.

• 폴리머
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• 제28권4호
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• pp.352-359
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• 2004

트립토판, 타이로신, 페닐알라닌과 같은 라세미 화합물의 광학 분할을 위해 광학 선택성 분리막을 이용한 막 분리법을 이용하였으며, 사용된 분리막 제조를 위해서 막 재료로 알진산나트륨 (sodium alginate)을, 가교제로 글루타르알데하이드 (glutaraldehyde)를 사용하였다. 제조된 막의 구조는 FT-IR을 이용하여 관찰하였고 라세미화합물의 광학 분할 메카니즘을 확인하기 위해서 모델링을 실시하였다. 막의 가교정도, 공급액의 농도, 조작압력, 그리고 공급액의 증류에 따른 막의 투과 특성을 알아보기 위해 여러 가지 변수를 통한 실험을 실시하였으며, 그 결과 막의 가교도와 두께가 증가할수록, 공급액의 농도와 용질의 크기가 감소할수록 즘 더 높은 광학 분할 능을 나타낸다는 것을 발견하였으며 이때의 enantiomeric excess (%ee) 값은 약 77%로 나타났다.